EP0424261B1 - Dyeing composition containing oxidation dyes precursors and aminoindole derivatives as coupling agent - Google Patents

Dyeing composition containing oxidation dyes precursors and aminoindole derivatives as coupling agent Download PDF

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Publication number
EP0424261B1
EP0424261B1 EP90402928A EP90402928A EP0424261B1 EP 0424261 B1 EP0424261 B1 EP 0424261B1 EP 90402928 A EP90402928 A EP 90402928A EP 90402928 A EP90402928 A EP 90402928A EP 0424261 B1 EP0424261 B1 EP 0424261B1
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Prior art keywords
amino
methyl
group
hydrogen atom
aminophenol
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German (de)
French (fr)
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EP0424261A1 (en
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Alex Junino
Gérard Lang
Jean Cotteret
Jean-Jacques Vandenbossche
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LOreal SA
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LOreal SA
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    • A—HUMAN NECESSITIES
    • A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61K—PREPARATIONS FOR MEDICAL, DENTAL OR TOILETRY PURPOSES
    • A61K8/00—Cosmetics or similar toiletry preparations
    • A61K8/18—Cosmetics or similar toiletry preparations characterised by the composition
    • A61K8/30—Cosmetics or similar toiletry preparations characterised by the composition containing organic compounds
    • A61K8/49—Cosmetics or similar toiletry preparations characterised by the composition containing organic compounds containing heterocyclic compounds
    • A—HUMAN NECESSITIES
    • A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61Q—SPECIFIC USE OF COSMETICS OR SIMILAR TOILETRY PREPARATIONS
    • A61Q5/00—Preparations for care of the hair
    • A61Q5/10—Preparations for permanently dyeing the hair
    • A—HUMAN NECESSITIES
    • A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61K—PREPARATIONS FOR MEDICAL, DENTAL OR TOILETRY PURPOSES
    • A61K8/00—Cosmetics or similar toiletry preparations
    • A61K8/18—Cosmetics or similar toiletry preparations characterised by the composition
    • A61K8/30—Cosmetics or similar toiletry preparations characterised by the composition containing organic compounds
    • A61K8/49—Cosmetics or similar toiletry preparations characterised by the composition containing organic compounds containing heterocyclic compounds
    • A61K8/4906—Cosmetics or similar toiletry preparations characterised by the composition containing organic compounds containing heterocyclic compounds with one nitrogen as the only hetero atom
    • A61K8/4913—Cosmetics or similar toiletry preparations characterised by the composition containing organic compounds containing heterocyclic compounds with one nitrogen as the only hetero atom having five membered rings, e.g. pyrrolidone carboxylic acid
    • A61K8/492—Cosmetics or similar toiletry preparations characterised by the composition containing organic compounds containing heterocyclic compounds with one nitrogen as the only hetero atom having five membered rings, e.g. pyrrolidone carboxylic acid having condensed rings, e.g. indol

Definitions

  • the present invention relates to new tinotorial compositions for keratin fibers and in particular for human hair. containing oxidation dye precursors and indole amino couplers, and dyeing methods using such compositions.
  • couplers also called color modifiers chosen more particularly from aromatic metadiamines, meta-aminophenols and metadiphenols.
  • Patent DE-A-1 916 139 describes dye compositions containing oxidation dye precursors of ortho or para type and, as couplers, indoline derivatives.
  • Patent USP 4,013,404 (PARENT) describes the use as an oxidation dye of certain aminoindoles alone or associated with couplers.
  • oxidation dye precursors or couplers are used to confer on the hair, in an oxidizing alkaline medium generally used in oxidation dyeing, a coloring having a satisfactory resistance to light, to washes, weathering and perspiration.
  • oxidation dye precursors or couplers are used to confer on the hair, in an oxidizing alkaline medium generally used in oxidation dyeing, a coloring having a satisfactory resistance to light, to washes, weathering and perspiration.
  • An object of the invention is constituted by dye oxidation compositions, intended to be used for dyeing keratin fibers; containing at least one para-type oxidation dye precursor, 6-methyl 1-hydroxy 2-aminobenzene and / or 4-methyl 1-amino 2-hydroxybenzene. with certain amino indole derivatives defined below.
  • Another object of the invention is constituted by the methods for coloring keratin fibers, in particular human hair, using such a composition.
  • the dyeing oxidation composition according to the invention intended to be used for dyeing keratin fibers, in particular human keratin fibers and in particular hair, is essentially characterized in that it contains in a suitable solvent medium for the dyeing of these fibers, at least one oxidation dye precursor of the para type 6-methyl 1-hydroxy 2-aminobenzene and / or 4-methyl 1-amino 2-hydroxybenzene.
  • R2 denotes a hydrogen atom, a C1-C4 alkyl group, a carboxyl group or an alkoxycarbonyl group; at least one of the radicals R2 or R3 denotes hydrogen;
  • R4 denotes a hydrogen atom or a C1-C4 alkyl or C1-C4 hydroxyalkyl or C2-C4 polyhydroxyalkyl group; the NHR4 group occupying positions 4, 6 or 7 of the benzene nucleus, as well as their salts.
  • the preferred compounds are those in which the alkyl radical denotes methyl, ethyl, the hydroxyalxyl radical denotes hydroxyethyl, the alkoxycarbonyl radical denotes methoxy- or ethoxycarbonyl.
  • R1, R2, R3 have the meanings indicated above and R4 denotes C1-C4 alkyl, C1-C4 hydroxyalkyl, C2-C4 polyhydroxyalkyl, R4NH occupying positions 4, 6 or 7 and R4 being different from alkyl when R4NH is in position 4.
  • the compound (II) is alkylated in a second step by the alkyl halide X-R4. When the alkyl halide is used in excess, a second group R4 is introduced.
  • the expected product (IA) is obtained by deformylation or detosylation of the compound (III), according to conventional methods.
  • 6-amino indole 7-amino indole, 6-N- ⁇ -hydroxyethylamino indole, 6-N- ⁇ -hydroxy-ethylamino 1-methyl indole, 6-methylamino indole, 6-amino N-methyl indole, 6-amino 2-carboxy indole, 6-amino 3-methyl indole, 6-amino 2-methyl indole, 6-amino 2-ethoxycarbonyl indole, 6-N ( ⁇ , ⁇ -dihydroxypropyl) amino indole.
  • Para dye precursors or 6-methyl 1-hydroxy 2-aminobenzene and 4-methyl 1-amino 2-hydroxybenzene are compounds which are not dyes in themselves, but which form dyes by a oxidative condensation process, either on themselves, or in the presence of a coupler or modifier.
  • para-type dye precursors are benzene or heterocyclic compounds which have two amino groups or else an amino group and a hydroxyl in the para position with respect to each other.
  • para-type dye precursors can be chosen from paraphenylenediamines, para-aminophenols, para heterocyclic precursors derived from pyridine or pyrimidine, such as 2,5-diaminopyridine, 2-hydroxy 5-aminopyridine, 2,4,5,6-tetraaminopyrimidine, so-called "double" bases.
  • the so-called double bases are bis-phenylalkylenediamines, corresponding to the formula: in which : Z1 and Z2, identical or different, represent hydroxyl groups or NHR3, where R3 denotes a hydrogen atom or a lower alkyl radical; R1 and R2, identical or different, represent either hydrogen atoms, or halogen atoms, or also alkyl groups; R represents a hydrogen atom, an alkyl, hydroxyalkyl or aminoalkyl group, the amino residue of which may be substituted; Y represents a radical taken from the group consisting of the following radicals: - (CH2) n -, (CH2) n , -O- (CH2) n , -, - (CH2) n , -CHOH- (CH2) n , - (CH2) n , n being an integer between 0 and 8 and n ′ an integer between 0 and 4, this base can be in the form of its addition salts with acids.
  • the alkyl or alkoxy radicals preferably denote a group having 1 to 4 carbon atoms and in particular methyl, ethyl, propyl, methoxy, ethoxy.
  • p-aminophenol 2-methyl 4-aminophenol, 3-methyl 4-aminophenol, 2-chloro 4-aminophenol, 3-chloro 4-aminophenol, 2.6 -dimethyl 4-aminophenol, 3,5-dimethyl 4-aminophenol, 2,3-dimethyl 4-aminophenol, 2,5-dimethyl 4-aminophenol, 2-hydroxy methyl 4-aminophenol, 2- ( ⁇ -hydroxyethyl) 4-aminophenol, 2-methoxy 4-aminophenol, 3-methoxy 4-aminophenol, 2-methoxymethyl 4-aminophenol.
  • N N'bis- ( ⁇ -hydroxyethyl) N, N'-bis (4'-amino phenyl) 1,3-diamino 2-propanol
  • N N 'bis- ( ⁇ -hydroxyethyl) N, N'-bis (4'-aminophenyl) ethylenediamine
  • N N' bis- (4-aminophenyl) tetramethylenediamine
  • N N'bis ( ⁇ -hydroxyethyl) N, N 'bis (4-aminophenyl) tetramethylene diamine
  • N N'bis (ethyl) N, N'-bis (4'-amino 3'-methyl- phenyl) ethylenediamine.
  • the dye compositions may also contain, in addition to the heterocyclic coupler corresponding to formula (I) above, other couplers known in themselves, such as metadiphenols, metaaminophenols, metaphenylenediamines, metaacylaminophenols, metaurideophenols, metacarbalcoxyaminophenols, ⁇ -naphthol, couplers having an active methylene group, such as ⁇ -ketone compounds and pyrazolones.
  • couplers having an active methylene group, such as ⁇ -ketone compounds and pyrazolones.
  • the concentration of compounds (I) can vary between 0.05 and 3.5% by weight relative to the total weight of the composition.
  • the solvent medium suitable for dyeing is generally aqueous and its pH can vary between 8 and 11 and it is preferably between 9 and 11.
  • basifying agents well known in the art, such as ammonia, alkali carbonates, alkanolamines such as mono-, di- or triethanolamine.
  • the dye compositions in accordance with the invention also contain, in their preferred embodiment, anionic, cationic, nonionic, amphoteric surfactants or mixtures thereof.
  • anionic, cationic, nonionic, amphoteric surfactants or mixtures thereof mention may be made of alkylbenzenesulfonates, alkylnaphthalene sulfonates, sulfates, ethersulfates and sulfonates of fatty alcohols, quaternary ammonium salts, such as trimethylketyl ammonium bromide, cetylpyridinium bromide, ethanolamides of optionally oxyethylenated fatty acids, polyoxyethylenated acids, alcohols or amines, polyglycerolated alcohols, polyoxyethylenated or polyglycerolated alkylphenols, as well as alkylsulphates polyoxyethylenated.
  • surfactants are present in the compositions in accordance with the invention in proportions of between 0.5 and 55% by weight, and preferably between 2 and 50% by weight relative to the total weight of the composition.
  • compositions can also contain organic solvents to dissolve the compounds which would not be sufficiently soluble in water.
  • organic solvents such as lower C1-C4 alkanols, such as ethanol and isopropanol; glycerol; glycols or glycol ethers, such as 2-butoxyethanol, ethylene glycol, propylene glycol, monoethyl ether and monomethyl ether of diethylene glycol, as well as aromatic alcohols such as benzyl alcohol or phenoxyethanol, analogous products or their mixtures.
  • the solvents are preferably present in a proportion of between 1 and 40% by weight, and in particular between 5 and 30% by weight relative to the total weight of the composition.
  • the thickening agents which can be added to the compositions in accordance with the invention can be chosen from sodium alginate, gum arabic or guar gum, cellulose derivatives, such as methylcellulose, hydroxyethylcellulose, hydroxypropylcellulose, hydroxymethylcellulose, carboxymethylcellulose, heterobiopolysaccharides, such as xanthan gum, polymers derived from acrylic acid.
  • Mineral thickeners can also be used, such as bentonite. These thickening agents are preferably present in proportions of between 0.1 and 5% and in particular between 0.2 and 3% by weight relative to the total weight of the composition.
  • the antioxidant agents which may be present in the compositions are chosen in particular from sodium sulfite, thioglycolic acid, sodium bisulfite, ascorbic acid, hydroquinone and homogentisic acid. These antioxidant agents are present in the composition in proportions of between 0.05 and 1.5% by weight relative to the total weight of the composition.
  • compositions can also contain other cosmetically acceptable adjuvants, such as, for example, penetration agents, sequestering agents, buffers, perfumes, etc.
  • compositions in accordance with the invention can be in various forms, such as in the form of liquids, creams, gels or in any other form suitable for dyeing keratin fibers and in particular that of human hair.
  • These compositions can be packaged in aerosol bottles in the presence of a propellant and form foams.
  • the dye compositions in accordance with the invention and containing a para-type oxidation dye precursor, 6-methyl 1-hydroxy 2-aminobenzene or / and 4-methyl 1-amino 2-hydroxybenzene. and a coupler of formula (I), are used according to a process implementing the development by an oxidizing agent.
  • the dye composition described above is mixed at the time of use with an oxidizing solution in an amount sufficient to be able to develop a coloring, then the mixture obtained is applied to the keratin fibers and in particular the hair. humans.
  • the oxidizing solution contains oxidizing agents, such as hydrogen peroxide, urea peroxide or persalts, such as ammonium persulfate.
  • oxidizing agents such as hydrogen peroxide, urea peroxide or persalts, such as ammonium persulfate.
  • the mixture obtained is applied to the hair and left to stand for 10 to 40 minutes, preferably 15 to 30 minutes, after which the hair is rinsed, washed with shampoo, rinsed again and dried.
  • the heterocyclic coupler of formula (I) defined above can also be used in a multistage process, consisting in one of the stages, in applying a para-oxidation dye precursor, 6-methyl 1- hydroxy 2-aminobenzene and / or 4-methyl 1-amino 2-hydroxy benzene and, in another step, to apply the coupler of formula (I).
  • the oxidizing agent can be introduced, just before application, into the composition applied in the second step or else be added to the keratin fibers themselves in a third step, the conditions for laying and drying or washing being identical.
  • a subject of the present invention is also the use of a heterocyclic compound of formula (I) defined above, as a coupler in the oxidation dyeing of keratin fibers using oxidation dye precursors of the type para or ortho such as 6-methyl 1-hydroxy 2-aminobenzene and 4-methyl 1-amino 2-hydroxybenzene.
  • the oily residue is taken up three times in 0.6 liters of isopropyl ether at reflux. Filter the ether and vacuum dry. The residual oil is taken up in 10 cm3 of ethyl acetate and purified on a silica column (eluent ethyl acetate 9 / Heptane 1).
  • the fraction containing the expected product is evaporated to dryness under vacuum.
  • compositions are prepared:
  • compositions are mixed weight by weight with an oxidizing agent titrating 20 volumes of hydrogen peroxide and whose pH is 3.
  • the mixtures thus produced are applied for 30 minutes to gray hair containing 90% white hairs, then rinsed and washed. The hair is then dried.
  • the following dye mixture is prepared: - p-phenylenediamine 0.27 g - 6-N- ( ⁇ , ⁇ -dihydroxypropyl) amino indole 0.52 g - Polyglycerolated oleic alcohol with 2 moles of glycerol 4.5g - Polyglycerolated oleic alcohol with 4 moles of glycerol 4.5g - ETHOMEEN O 12 - ARMOON HESS CHEMICAL Ltd (oxyethylenated oleylamine with 12 modes of ethylene oxide) 4.5g - COMPERLAN KD - HENKEL Company (coconut diethanolamide) 9.0 g - Propylene glycol 4.0g - 2-butoxyethanol 8.0 g - 96 ° ethanol 6.0 g - MASQUOL DTPA - PROTEX Company (pentasodium salt of diethylene triamine pentacetic acid) 2.0 g - Hydroquinone 0.15 g - Sodium

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  • Indole Compounds (AREA)
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  • Non-Silver Salt Photosensitive Materials And Non-Silver Salt Photography (AREA)
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Abstract

Oxidation dyeing composition intended for use for dyeing keratinous fibres, especially human keratinous fibres, and in particular the hair, which contains, in a solvent medium suitable for dyeing these fibres, at least one para oxidation dye precursor or at least one ortho oxidation dye precursor and at least one heterocyclic coupler corresponding to the formula (I): <IMAGE> in which: R1 and R3, which may be identical or different, denote a hydrogen atom or a C1-C4 alkyl group; R2 denotes a hydrogen atom, a C1-C4 alkyl group, a carboxyl group or an alkoxycarbonyl group; at least one of the radicals R2 or R3 denoting hydrogen; R4 denotes a hydrogen atom or a C1-C4 alkyl or C1-C4 hydroxyalkyl or C2-C4 polyhydroxyalkyl group; the group NHR4 occupying positions 4, 6 or 7 of the benzene ring, as well as their salts.

Description

La présente invention est relative à de nouvelles compositions tinotoriales pour fibres kératiniques et en particulier pour cheveux humains. contenant des précurseurs de colorants d'oxydation et des coupleurs amino indoliques, et procédés de teinture mettant en oeuvre de telles compositions.The present invention relates to new tinotorial compositions for keratin fibers and in particular for human hair. containing oxidation dye precursors and indole amino couplers, and dyeing methods using such compositions.

Il est connu de teindre les fibres kératiniques et en particulier les cheveux humains, avec des compositions tinotoriales contenant des précurseurs de colorants d'oxydation, en particulier des p-phénylène diamines, des ortho- ou para-aminophénols qu'on appelle généralement "bases d'oxydation".It is known to dye keratin fibers and in particular human hair, with tinotorial compositions containing precursors of oxidation dyes, in particular p-phenylene diamines, ortho- or para-aminophenols which are generally called "bases". oxidation ".

On sait également qu'on peut faire varier les nuances obtenues avec ces bases d'oxydation en utilisant, en association avec ces bases, des coupleurs encore appelés modificàteurs de coloration choisis plus particulièrement parmi les métadiamines aromatiques, les méta-aminophénols et les métadiphénols.We also know that the shades obtained with these oxidation bases can be varied by using, in combination with these bases, couplers also called color modifiers chosen more particularly from aromatic metadiamines, meta-aminophenols and metadiphenols.

Le brevet DE-A-1 916 139 décrit des compositions tinctoriales contenant des précurseurs de colorant d'oxydation de type ortho ou para et, en tant que coupleurs, des dérivés indolines.Patent DE-A-1 916 139 describes dye compositions containing oxidation dye precursors of ortho or para type and, as couplers, indoline derivatives.

Le brevet USP 4 013 404 (PARENT) décrit l'utilisation en tant que colorant d'oxydation de certains aminoindoles seuls ou associés à des coupleurs.Patent USP 4,013,404 (PARENT) describes the use as an oxidation dye of certain aminoindoles alone or associated with couplers.

On recherche, dans le domaine de la teinture capillaire, des précurseurs de colorants d'oxydation ou des coupleurs permettant de conferer aux cheveux, en milieu alcalin oxydant généralement utilise en teinture d'oxydation, une coloration ayant une résistance satisfaisante à la lumière, aux lavages, aux intempéries et à la transpiration. On souhaite également obtenir des couleurs avec des reflets, ce qui, en teinture d'oxydation, nécessite l'emploi de colorants directs stables en milieu réducteur.In the field of hair dyeing, oxidation dye precursors or couplers are used to confer on the hair, in an oxidizing alkaline medium generally used in oxidation dyeing, a coloring having a satisfactory resistance to light, to washes, weathering and perspiration. We also want to obtain colors with reflections, which, in oxidation dyeing, requires the use of direct dyes stable in a reducing medium.

La demanderesse vient de découvrir de manière suprenante, ce qui fait l'objet de l'invention, que l'utilisation de certains dérivés indoliques à titre de coupleurs, avec des précurseurs de colorants d'oxydation de type para ou ortho, permettait d'obtenir après application sur les fibres kératiniques et en particulier les cheveux, des couleurs avec reflets présentant des résistances à la lumière, aux lavages, aux intempéries et à la transpiration, particulairement remarquables.The Applicant has just discovered, surprisingly, which is the subject of the invention, that the use of certain indole derivatives as couplers, with oxidation dye precursors of the para or ortho type, made it possible to obtain after application to keratin fibers and in particular the hair, colors with reflections having resistance to light, washing, weathering and perspiration, particularly remarkable.

Un objet de l'invention est constitue par des compositions tinctoriales d'oxydation, destinées à être utilisées pour la teinture des fibres kératiniques; contenant au moins un précurseur de colorant d'oxydation de type para, le 6-méthyl 1-hydroxy 2-aminobenzène et/ou le 4-méthyl 1-amino 2-hydroxybenzène. avec certains dérivés amino indoliques définis ci-après.An object of the invention is constituted by dye oxidation compositions, intended to be used for dyeing keratin fibers; containing at least one para-type oxidation dye precursor, 6-methyl 1-hydroxy 2-aminobenzene and / or 4-methyl 1-amino 2-hydroxybenzene. with certain amino indole derivatives defined below.

Un autre objet ce l'invention est constitué par les procédés de coloration des fibres kératiniques, en particulier des cheveux humains, mettant en oeuvre une telle composition.Another object of the invention is constituted by the methods for coloring keratin fibers, in particular human hair, using such a composition.

D'autres objets de l'invention apparaîtront à la lecture ce la description et des exemples qui suivent.Other objects of the invention will appear on reading this description and examples which follow.

La composition tinctoriale d'oxydation conforme a l'invention, destinée à être utilisée pour la teinture des fibres kératiniques, en particulier des fibres kératiniques humaines et notamment des cheveux, est essentiellement caractérisée par le fait qu'elle contient dans un milieu solvant approprie pour la teinture de ces fibres, au moins un précurseur de colorant d'oxydation de type para le 6-méthyl 1-hydroxy 2-aminobenzène et/ou le 4-méthyl 1-amino 2-hydroxybenzène. et au moins un coupleur hétérocyclique, répondant à la formule (I) :

Figure imgb0001

dans laquelle :
   R₁ et R₃, identiques ou différents, désignent un atome d'hydrogène, un groupement alkyle en C₁-C₄;
   R₂ désigne un atome d'hydrogène, un groupement alkyle en C₁-C₄, un groupement carboxyle ou un groupement alcoxycarbonyle; au moins l'un des radicaux R₂ ou R₃ désigne hydrogène;
   R₄ désigne un atome d'hydrogène ou un groupement alkyle en C₁-C₄ ou hydroxyalkyle en C₁-C₄ ou polyhydroxyalkyle en C₂-C₄;
   le groupement NHR₄ occupant les positions 4, 6 ou 7 du noyau benzénique, ainsi que leurs sels.The dyeing oxidation composition according to the invention, intended to be used for dyeing keratin fibers, in particular human keratin fibers and in particular hair, is essentially characterized in that it contains in a suitable solvent medium for the dyeing of these fibers, at least one oxidation dye precursor of the para type 6-methyl 1-hydroxy 2-aminobenzene and / or 4-methyl 1-amino 2-hydroxybenzene. and at least one heterocyclic coupler, corresponding to formula (I):
Figure imgb0001
in which :
R₁ and R₃, identical or different, denote a hydrogen atom, a C₁-C₄ alkyl group;
R₂ denotes a hydrogen atom, a C₁-C₄ alkyl group, a carboxyl group or an alkoxycarbonyl group; at least one of the radicals R₂ or R₃ denotes hydrogen;
R₄ denotes a hydrogen atom or a C₁-C₄ alkyl or C₁-C₄ hydroxyalkyl or C₂-C₄ polyhydroxyalkyl group;
the NHR₄ group occupying positions 4, 6 or 7 of the benzene nucleus, as well as their salts.

Parmi les composes de formule (I), les composés préférés sont ceux dans lesquels le radical alkyle désigne méthyle, éthyle, le radical hydroxyalxyle désigne hydroxyéthyle, le radical alcoxycarbonyle désigne méthoxy- ou éthoxycarbonyle.Among the compounds of formula (I), the preferred compounds are those in which the alkyl radical denotes methyl, ethyl, the hydroxyalxyl radical denotes hydroxyethyl, the alkoxycarbonyl radical denotes methoxy- or ethoxycarbonyl.

Parmi les composes de formule (I), ceux repondant à la formule (IA) sont nouveaux et ceci constitue un autre objet de l'invention.

Figure imgb0002

dans laquelle R₁, R₂, R₃ ont les significations indiquées ci-dessus et R₄ désigne alkyle en C₁-C₄, hydroxyalkyle en C₁-C₄, polyhydroxyalkyle en C₂-C₄, R₄NH occupant les positions 4, 6 ou 7 et R₄ étant différent d'alkyle lorsque R₄NH est en position 4.Among the compounds of formula (I), those corresponding to formula (IA) are new and this constitutes another object of the invention.
Figure imgb0002
in which R₁, R₂, R₃ have the meanings indicated above and R₄ denotes C₁-C₄ alkyl, C₁-C₄ hydroxyalkyl, C₂-C₄ polyhydroxyalkyl, R₄NH occupying positions 4, 6 or 7 and R₄ being different from alkyl when R₄NH is in position 4.

Ces composés de formule (IA) peuvent être préparés selon le procédé suivant.These compounds of formula (IA) can be prepared according to the following process.

Le composé (IA) est obtenu à partir du composé (IB) (R₄=H) par les méthodes de substitution des amines aromatiques, selon le schéma réactionnel :

Figure imgb0003

   Par formylation ou tosylation, on obtient le compose (II). Le composé (II) est alkyle dans un deuxième temps par l'halogénure d'alkyle X-R₄. Lorsque l'halogénure d'alkyle est utilise en exces, un second groupement R₄ est introduit. Le produit attendu (IA) est obtenu par déformylation ou détosylation du composé (III), selon les méthodes conventionnelles.The compound (IA) is obtained from the compound (IB) (R₄ = H) by the methods of substitution of aromatic amines, according to the reaction scheme:
Figure imgb0003
By formylation or tosylation, the compound (II) is obtained. The compound (II) is alkylated in a second step by the alkyl halide X-R₄. When the alkyl halide is used in excess, a second group R₄ is introduced. The expected product (IA) is obtained by deformylation or detosylation of the compound (III), according to conventional methods.

Parmi les méthodes d'hydroxyéthylation, on peut citer l'action du chloroformiate de β-chloréthyle sur le composé (IB) qui permet d'obtenir dans un premier temps le carbamate de β-chloréthyle correspondant qui, soumis dans un deuxième temps à l'action d'une base minérale forte, permet d'obtenir le compose (IA) pour lequel le radical R₄ est un radical β-hydroxyéthyle.Among the hydroxyethylation methods, mention may be made of the action of β-chloroethyl chloroformate on the compound (IB) which makes it possible first to obtain the corresponding β-chloroethyl carbamate which, subsequently subjected to l action of a strong mineral base, makes it possible to obtain the compound (IA) for which the radical R₄ is a β-hydroxyethyl radical.

Parmi les composés de formule (I), on peut citer le 6-amino indole, le 7-amino indole, le 6-N-β-hydroxyéthylamino indole, le 6-N-β-hydroxy-éthylamino 1-méthyl indole, le 6-méthylamino indole, le 6-amino N-méthyl indole, le 6-amino 2-carboxy indole, le 6-amino 3-méthyl indole, le 6-amino 2-méthyl indole, le 6-amino 2-éthoxycarbonyl indole, le 6-N(β, γ-dihydroxypropyl)amino indole.Among the compounds of formula (I), mention may be made of 6-amino indole, 7-amino indole, 6-N-β-hydroxyethylamino indole, 6-N-β-hydroxy-ethylamino 1-methyl indole, 6-methylamino indole, 6-amino N-methyl indole, 6-amino 2-carboxy indole, 6-amino 3-methyl indole, 6-amino 2-methyl indole, 6-amino 2-ethoxycarbonyl indole, 6-N (β, γ-dihydroxypropyl) amino indole.

Parmi ces composes, on notera que, par couplage oxydatif avec les précurseurs de colorants définis ci-après, le 6-amino indole et ses dérivés conduisent à des nuances à dominantes cuivrées (nuances chaudes); et que le 7-amino indole et ses dérivés conduisent à des nuances à reflets cendres ou acajou.Among these compounds, it will be noted that, by oxidative coupling with the dye precursors defined below, 6-amino indole and its derivatives lead to copper-dominant shades (warm shades); and that 7-amino indole and its derivatives lead to shades with ash or mahogany reflections.

Les précurseurs de colorants de type para ou le 6-méthyl 1-hydroxy 2-aminobenzène et le 4-méthyl 1-amino 2-hydroxybenzène sont des composés qui ne sont pas des colorants en eux-mêmes, mais qui forment des colorants par un processus de condensation oxydative, soit sur eux-mêmes, soit en présence d'un coupleur ou modificateur.Para dye precursors or 6-methyl 1-hydroxy 2-aminobenzene and 4-methyl 1-amino 2-hydroxybenzene are compounds which are not dyes in themselves, but which form dyes by a oxidative condensation process, either on themselves, or in the presence of a coupler or modifier.

Ces précurseurs de colorants de type para sont des composés benzéniques ou hétérocycliques qui comportent deux groupements amino ou bien un groupement amino et un hydroxyle en position para l'un par rapport à l'autre.These para-type dye precursors are benzene or heterocyclic compounds which have two amino groups or else an amino group and a hydroxyl in the para position with respect to each other.

Ces précurseurs de colorants de type para peuvent être choisis parmi les paraphénylènediamines, les para-aminophénols, les précurseurs hétérocycliques para dérivés de la pyridine ou de la pyrimidine, tels que la 2,5-diaminopyridine, la 2-hydroxy 5-aminopyridine, la 2,4,5,6-tétraaminopyrimidine, des bases dites "doubles".These para-type dye precursors can be chosen from paraphenylenediamines, para-aminophenols, para heterocyclic precursors derived from pyridine or pyrimidine, such as 2,5-diaminopyridine, 2-hydroxy 5-aminopyridine, 2,4,5,6-tetraaminopyrimidine, so-called "double" bases.

A titre de paraphénylènediamines, on peut plus particulièrement citer les composés répondant à la formule (II) ci-après :

Figure imgb0004

dans laquelle :
   R₅, R₆ et R₇, identiques ou différents, représentent un atome d'hydrogène ou d'halogène, un radical alkyle, un radical alcoxy;
   R₈ et R₉, identiques ou différents, représentent un atome d'hydrogène, un radical alkyle, hydroxyalkyle, alcoxyalkyle, carbamylalkyle, mésylamino alkyle, acétylaminoalkyle, uréidoalkyle, carbalcoxyamino alkyle, pipéridinoalkyle, morpholinoalkyle; ou bien R₈ et R₉ forment, conjointement avec l'atome d'azote auquel ils sont liés, un hétérocycle pipéridino ou morpholino, sous reserve que R₅ ou R₇ représente un atome d'hydrogène lorsque R₈ et R₉ ne représentent pas un atome d'hydrogène;
   ainsi que les sels de ces composés.Mention may more particularly be made, as paraphenylenediamines, of the compounds corresponding to formula (II) below:
Figure imgb0004
in which :
R₅, R₆ and R₇, identical or different, represent a hydrogen or halogen atom, an alkyl radical, an alkoxy radical;
R₈ and R₉, identical or different, represent a hydrogen atom, an alkyl, hydroxyalkyl, alkoxyalkyl, carbamylalkyl, mesylamino alkyl, acetylaminoalkyl, ureidoalkyl, carbalkoxyaminoalkyl, piperidinoalkyl, morpholinoalkyl radical; or else R₈ and R₉ form, together with the nitrogen atom to which they are linked, a piperidino or morpholino heterocycle, provided that R₅ or R₇ represents an atom hydrogen when R₈ and R₉ do not represent a hydrogen atom;
as well as the salts of these compounds.

Les bases dites doubles sont des bis-phénylalkylènediamines, répondant à la formule :

Figure imgb0005

dans laquelle :
   Z₁ et Z₂, identiques ou différents, représentent des groupements hydroxyle ou NHR₃, où R₃ désigne un atome d'hydrogène ou un radical alcoyle inférieur;
   R₁ et R₂, identiques ou différents, représentent soit des atomes d'hydrogène, soit des atomes d'halogène, soit encore des groupements alcoyle;
   R représente un atome d'hydrogène, un groupe alcoyle, hydroxyalcoyle ou aminoalcoyle, dont le reste amino peut être substitué;
   Y représente un radical pris dans le groupe constitué par les radicaux suivants : -(CH₂)n-, (CH₂)n, -O-(CH₂)n,-, -(CH₂)n,-CHOH- (CH₂)n,-(CH₂)n,
Figure imgb0006
n étant un nombre entier compris entre 0 et 8 et n′ un nombre entier compris entre 0 et 4, cette base pouvant se présenter sous forme de ses sels d'addition avec des acides.The so-called double bases are bis-phenylalkylenediamines, corresponding to the formula:
Figure imgb0005
in which :
Z₁ and Z₂, identical or different, represent hydroxyl groups or NHR₃, where R₃ denotes a hydrogen atom or a lower alkyl radical;
R₁ and R₂, identical or different, represent either hydrogen atoms, or halogen atoms, or also alkyl groups;
R represents a hydrogen atom, an alkyl, hydroxyalkyl or aminoalkyl group, the amino residue of which may be substituted;
Y represents a radical taken from the group consisting of the following radicals: - (CH₂) n -, (CH₂) n , -O- (CH₂) n , -, - (CH₂) n , -CHOH- (CH₂) n , - (CH₂) n ,
Figure imgb0006
n being an integer between 0 and 8 and n ′ an integer between 0 and 4, this base can be in the form of its addition salts with acids.

Les radicaux alkyle ou alcoxy désignent de préférence un groupement ayant 1 à 4 atomes de carbone et notamment méthyle, éthyle, propyle, méthoxy, éthoxy.The alkyl or alkoxy radicals preferably denote a group having 1 to 4 carbon atoms and in particular methyl, ethyl, propyl, methoxy, ethoxy.

Parmi les composés de formule (II), on peut citer en particulier la p-phénylènediamine, la p-toluylènediamine, la méthoxyparaphénylènediamine, la 2,6-diméthyl p-phénylènediamine, la 2,5-diméthyl p-phénylènediamine, la 2-méthyl 5-méthoxy paraphénylènediamine, la 2,6-diméthyl 5-méthoxy p-phénylènediamine, la N,N-diméthylparaphénylènediamine, la 3-méthyl 4-amino N,N-diéthylaniline, la N,N-di(β-hydroxyéthyl)paraphénylènediamine, la 3-méthyl 4-amino N,N-di-(β-hydroxyéthyl)aniline, la 3-chloro 4-amino N,N-di-(β-hydroxyéthyl)aniline, la 4-amino N,N-(éthylcarbamylméthyl)aniline, la 3-méthyl 4-amino N,N-(éthylcarbamylméthyl)aniline, la 4-amino N,N-(éthyl β-pipéridinoéthyl)aniline, la 3-méthyl 4-amino N,N-(éthyl,β-pipéridinoéthyl)aniline, la 4-amino N,N-(éthyl,β-morpholinoéthyl)aniline, la 3-méthyl 4-amino N,N-(éthyl,β-morpholinoéthyl)aniline, la 4-amino N,N-(éthyl,β-acétylaminoéthyl)aniline, la 4-amino N-(β-méthoxyéthyl)aniline, la 3-méthyl 4-amino N,N-(éthyl,β-acétylaminoéthyl)aniline, la 4-amino N,N-(éthyl,β-mésylaminoéthyl)aniline, la 3-méthyl 4-amino N,N-(éthyl,β-mésylaminoéthyl)aniline, la 4-amino N,N-(éthyl,β-sulfoéthyl)aniline, la 3-méthyl 4-amino N,N-(éthyl,β-sulfoéthyl)aniline,la N-[(4′-amino)phényl]morpholine, la N-[(4′-amino)phényl]pipéridine. Ces précurseurs de colorants par oxydation de type para peuvent être introduits dans la composition tinctoriale, soit sous forme de base libre, soit sous forme de sels, tels que sous forme de chlorhydrate, de bromhydrate ou de sulfate.Among the compounds of formula (II), mention may be made in particular of p-phenylenediamine, p-toluylenediamine, methoxyparaphenylenediamine, 2,6-dimethyl p-phenylenediamine, 2,5-dimethyl p-phenylenediamine, 2-methyl 5-methoxy paraphenylenediamine, 2,6-dimethyl 5-methoxy p-phenylenediamine, N, N-dimethylparaphenylenediamine, 3-methyl 4-amino N, N-diethylaniline, N, N-di (β-hydroxyethyl) paraphenylenediamine, 3-methyl 4-amino N, N-di- (β-hydroxyethyl) aniline, 3-chloro 4-amino N, N-di- (β-hydroxyethyl) aniline, 4-amino N, N- (ethylcarbamylmethyl) aniline, 3-methyl 4-amino N, N- (ethylcarbamylmethyl) aniline , 4-amino N, N- (ethyl β-piperidinoethyl) aniline, 3-methyl 4-amino N, N- (ethyl, β-piperidinoethyl) aniline, 4-amino N, N- (ethyl, β- morpholinoethyl) aniline, 3-methyl 4-amino N, N- (ethyl, β-morpholinoethyl) aniline, 4-amino N, N- (ethyl, β-acetylaminoethyl) aniline, 4-amino N- (β- methoxyethyl) aniline, 3-methyl 4-amino N, N- (ethyl, β-acetylaminoethyl) aniline, 4-amino N, N- (ethyl, β-mesyla minoethyl) aniline, 3-methyl 4-amino N, N- (ethyl, β-mesylaminoethyl) aniline, 4-amino N, N- (ethyl, β-sulfoethyl) aniline, 3-methyl 4-amino N, N- (ethyl, β-sulfoethyl) aniline, N - [(4′-amino) phenyl] morpholine, N - [(4′-amino) phenyl] piperidine. These para-oxidation dye precursors can be introduced into the dye composition, either in the form of a free base or in the form of salts, such as in the form of hydrochloride, hydrobromide or sulfate.

Parmi les p-aminophénols, on peut citer le p-aminophénol, le 2-méthyl 4-aminophénol, le 3-méthyl 4-aminophénol, le 2-chloro 4-aminophénol, le 3-chloro 4-aminophénol, le 2,6-diméthyl 4-aminophénol, le 3,5-diméthyl 4-aminophénol, le 2,3-diméthyl 4-aminophénol, le 2,5-diméthyl 4-aminophénol, le 2-hydroxy méthyl 4-aminophénol, le 2-(β-hydroxyéthyl)4-aminophénol, le 2-méthoxy 4-aminophénol, le 3-méthoxy 4-aminophénol, le 2-méthoxyméthyl 4-aminophénol.Among the p-aminophenols, there may be mentioned p-aminophenol, 2-methyl 4-aminophenol, 3-methyl 4-aminophenol, 2-chloro 4-aminophenol, 3-chloro 4-aminophenol, 2.6 -dimethyl 4-aminophenol, 3,5-dimethyl 4-aminophenol, 2,3-dimethyl 4-aminophenol, 2,5-dimethyl 4-aminophenol, 2-hydroxy methyl 4-aminophenol, 2- (β -hydroxyethyl) 4-aminophenol, 2-methoxy 4-aminophenol, 3-methoxy 4-aminophenol, 2-methoxymethyl 4-aminophenol.

Parmi les composés de formule (IIbis), on peut citer le N,N'bis-(β-hydroxyéthyl)N,N'-bis(4'-amino phenyl)1,3-diamino 2-propanol, la N,N'bis-(β-hydroxyethyl)N,N'-bis(4'-aminophenyl)éthylènediamine, la N,N' bis-(4-aminophenyl)tétraméthylènediamine, la N,N'bis(β-hydroxyéthyl)N,N'bis(4-aminophényl)tétraméthylène diamine, la N,N'bis-(4-méthylaminophényl)tétraméthylène diamine, la N,N'bis(éthyl)N,N'-bis(4'-amino 3'-methyl-phényl)éthylènediamine.Among the compounds of formula (IIbis), there may be mentioned N, N'bis- (β-hydroxyethyl) N, N'-bis (4'-amino phenyl) 1,3-diamino 2-propanol, N, N 'bis- (β-hydroxyethyl) N, N'-bis (4'-aminophenyl) ethylenediamine, N, N' bis- (4-aminophenyl) tetramethylenediamine, N, N'bis (β-hydroxyethyl) N, N 'bis (4-aminophenyl) tetramethylene diamine, N, N'bis- (4-methylaminophenyl) tetramethylene diamine, N, N'bis (ethyl) N, N'-bis (4'-amino 3'-methyl- phenyl) ethylenediamine.

Les compositions tinctoriales peuvent egalement contenir en plus du coupleur hétérocyclique répondant à la formule (I) ci-dessus, d'autres coupleurs connus en eux-mêmes, tels que les métadiphenols, les métaaminophénols, les métaphénylènediamines, les métaacylaminophénols, les métauréidophénols, les métacarbalcoxyaminophénols, l'α-naphtol, les coupleurs possédant un groupe méthylène actif, tels que les composés β-cétoniques et les pyrazolones.The dye compositions may also contain, in addition to the heterocyclic coupler corresponding to formula (I) above, other couplers known in themselves, such as metadiphenols, metaaminophenols, metaphenylenediamines, metaacylaminophenols, metaurideophenols, metacarbalcoxyaminophenols, α-naphthol, couplers having an active methylene group, such as β-ketone compounds and pyrazolones.

On peut citer plus particulièrement, à titre d'exemple, le 2,4-dihydroxy phénoxyéthanol, le 2,4-dihydroxy anisole, le métaaminophénol, le monométhyl éther de résorcine, le 2-méthyl 5-aminophénol, le 2-méthyl 5-N-(β-hydroxyéthyl)aminophénol, le 2-méthyl 5-N-(β-mésylaminoéthyl)aminophénol, le 2,6-diméthyl 3-aminophénol, la 6-hydroxybenzomorpholine, le 2,4-diamino anisole, le 2,4-diaminophénoxyéthanol, la 6-aminobenzomorpholine, le 2-[N-(β-hydroxyéthyl)amino 4-amino]phénoxyéthanol, le 2-amino 4-N-(β-hydroxyéthyl) amino anisole, le (2,4-diamino)phényl,β, γ-dihydroxy propyléther, la 2,4-diaminophénoxyéthylamine, et leurs sels.Mention may more particularly be made, by way of example, of 2,4-dihydroxy phenoxyethanol, 2,4-dihydroxy anisole, metaaminophenol, monomethyl ether of resorcinol, 2-methyl 5-aminophenol, 2-methyl 5 -N- (β-hydroxyethyl) aminophenol, 2-methyl 5-N- (β-mesylaminoethyl) aminophenol, 2,6-dimethyl 3-aminophenol, 6-hydroxybenzomorpholine, 2,4-diamino anisole, 2 , 4-diaminophenoxyethanol, 6-aminobenzomorpholine, 2- [N- (β-hydroxyethyl) amino 4-amino] phenoxyethanol, 2-amino 4-N- (β-hydroxyethyl) amino anisole, (2,4- diamino) phenyl, β, γ-dihydroxy propylether, 2,4-diaminophenoxyethylamine, and their salts.

On peut rajouter à ces compositions, comme cela est bien connu dans l'état de la technique, des colorants directs, tels que des colorants azoïques, anthraquinoniques ou les dérivés nitrés de la série benzénique.It is possible to add to these compositions, as is well known in the state of the art, direct dyes, such as azo dyes, anthraquinones or nitro derivatives of the benzene series.

L'ensemble des précurseurs de colorants par oxydation de type para, le 6-méthyl 1-hydroxy 2-aminobenzène et/ou le 4-méthyl 1-amino 2-hydroxybenzène. ainsi que les coupleurs utilises dans les compositions tinctoriales conformement à l'invention, représente de préférence de 0,3 à 7% en poids par rapport au poids total de la composition. La concentration en composes (I) peut varier entre 0,05 et 3,5% en poids par rapport au poids total de la composition.All of the para-oxidation dye precursors, 6-methyl 1-hydroxy 2-aminobenzene and / or 4-methyl 1-amino 2-hydroxybenzene. as well as the couplers used in the dye compositions in accordance with the invention, preferably represents from 0.3 to 7% by weight relative to the total weight of the composition. The concentration of compounds (I) can vary between 0.05 and 3.5% by weight relative to the total weight of the composition.

Le milieu solvant approprie pour la teinture est généralement aqueux et son pH peut varier entre 8 et 11 et il est de préférence compris entre 9 et 11.The solvent medium suitable for dyeing is generally aqueous and its pH can vary between 8 and 11 and it is preferably between 9 and 11.

Il est ajuste à la valeur désirée à l'aide d'agents alcalinisants bien connus dans l'état de la technique, tels que l'ammoniaque, les carbonates alcalins, les alcanolamines comme la mono-, la di- ou la triéthanolamine.It is adjusted to the desired value using basifying agents well known in the art, such as ammonia, alkali carbonates, alkanolamines such as mono-, di- or triethanolamine.

Les compositions tinctoriales conformes à l'invention contiennent également dans leur forme de réalisation préférée, des agents tensio-actifs anioniques, cationiques, non ioniques, amphotères ou leurs mélanges. Parmi ces agents tensio-actifs, on peut citer les alkylbenzènesulfonates, les alkylnaphtalène sulfonates, les sulfates, les éthersulfates et les sulfonates d'alcools gras, les sels d'ammonium quaternaires, tels que le bromure de triméthylcétyl ammonium, le bromure de cétylpyridinium, les éthanolamides d'acides gras éventuellement oxyéthylénés, les acides, les alcools ou les amines polyoxyéthylénés, les alcools polyglycérolés, les alkylphènols polyoxy éthylénés ou polyglycérolés, ainsi que les alkylsulfates polyoxyéthylénés.The dye compositions in accordance with the invention also contain, in their preferred embodiment, anionic, cationic, nonionic, amphoteric surfactants or mixtures thereof. Among these surfactants, mention may be made of alkylbenzenesulfonates, alkylnaphthalene sulfonates, sulfates, ethersulfates and sulfonates of fatty alcohols, quaternary ammonium salts, such as trimethylketyl ammonium bromide, cetylpyridinium bromide, ethanolamides of optionally oxyethylenated fatty acids, polyoxyethylenated acids, alcohols or amines, polyglycerolated alcohols, polyoxyethylenated or polyglycerolated alkylphenols, as well as alkylsulphates polyoxyethylenated.

Ces agents tensio-actifs sont présents dans les compositions conformes à l'invention dans des proportions comprises entre 0,5 et 55% en poids, et de préférence entre 2 et 50% en poids par rapport au poids total de la composition.These surfactants are present in the compositions in accordance with the invention in proportions of between 0.5 and 55% by weight, and preferably between 2 and 50% by weight relative to the total weight of the composition.

Ces compositions peuvent également contenir des solvants organiques pour solubiliser les composés qui ne seraient pas suffisamment solubles dans l'eau. Parmi ces solvants, on peut citer à titre d'exemple, les alcanols inférieurs en C₁-C₄, tels que l'éthanol et l'isopropanol; le glycérol; les glycols ou éthers de glycols, comme le 2-butoxyéthanol, l'éthylèneglycol, le propylèneglycol, le monoéthyléther et le monométhyléther du diéthylèneglycol, ainsi que les alcools aromatiques comme l'alcool benzylique ou le phénoxyéthanol, les produits analogues ou leurs mélanges.These compositions can also contain organic solvents to dissolve the compounds which would not be sufficiently soluble in water. Among these solvents, mention may be made, by way of example, of lower C₁-C₄ alkanols, such as ethanol and isopropanol; glycerol; glycols or glycol ethers, such as 2-butoxyethanol, ethylene glycol, propylene glycol, monoethyl ether and monomethyl ether of diethylene glycol, as well as aromatic alcohols such as benzyl alcohol or phenoxyethanol, analogous products or their mixtures.

Les solvants sont présents de préférence dans une proportion comprise entre 1 et 40% en poids, et en particulier entre 5 et 30% en poids par rapport au poids total de la composition.The solvents are preferably present in a proportion of between 1 and 40% by weight, and in particular between 5 and 30% by weight relative to the total weight of the composition.

Les agents épaississants que l'on peut ajouter dans les compositions conformes à l'invention peuvent être choisis parmi l'alginate de sodium, la gomme arabique ou la gomme de guar, les dérivés de cellulose, tels que la méthylcellulose, l'hydroxyéthylcellulose, l'hydroxypropylcellulose, l'hydroxyméthylcellulose, la carboxyméthylcellulose, les hétérobiopolysaccharides, tels que la gomme de xanthane, les polymères dérivés d'acide acrylique. On peut également utiliser des agents épaississants minéraux, tels que la bentonite. Ces agents épaississants sont présents de préférence dans des proportions comprises entre 0,1 et 5% et en particulier entre 0,2 et 3% en poids par rapport au poids total de la composition.The thickening agents which can be added to the compositions in accordance with the invention can be chosen from sodium alginate, gum arabic or guar gum, cellulose derivatives, such as methylcellulose, hydroxyethylcellulose, hydroxypropylcellulose, hydroxymethylcellulose, carboxymethylcellulose, heterobiopolysaccharides, such as xanthan gum, polymers derived from acrylic acid. Mineral thickeners can also be used, such as bentonite. These thickening agents are preferably present in proportions of between 0.1 and 5% and in particular between 0.2 and 3% by weight relative to the total weight of the composition.

Les agents antioxydants qui peuvent être présents dans les compositions sont choisis en particulier parmi le sulfite de sodium, l'acide thioglycolique, le bisulfite de sodium, l'acide ascorbique, l'hydroquinone et l'acide homogentisique. Ces agents antioxydants sont présents dans la composition dans des proportions comprises entre 0,05 et 1,5% en poids par rapport au poids total de la composition.The antioxidant agents which may be present in the compositions are chosen in particular from sodium sulfite, thioglycolic acid, sodium bisulfite, ascorbic acid, hydroquinone and homogentisic acid. These antioxidant agents are present in the composition in proportions of between 0.05 and 1.5% by weight relative to the total weight of the composition.

Ces compositions peuvent également contenir d'autres adjuvants cosmétiquement acceptables, tels que par exemple des agents de pénétration, des agents séquestrants, des tampons, des parfums, etc.These compositions can also contain other cosmetically acceptable adjuvants, such as, for example, penetration agents, sequestering agents, buffers, perfumes, etc.

Les compositions conformes à l'invention peuvent se présenter sous des formes diverses, telles que sous forme de liquides, de crèmes, de gels ou sous toute autre forme appropriée pour réaliser une teinture des fibres kératiniques et notamment celle des cheveux humains. Ces compositions peuvent être conditionnées en flacons aerosols en présence d'un agent propulseur et former des mousses.The compositions in accordance with the invention can be in various forms, such as in the form of liquids, creams, gels or in any other form suitable for dyeing keratin fibers and in particular that of human hair. These compositions can be packaged in aerosol bottles in the presence of a propellant and form foams.

Les compositions tinctoriales conformes a l'invention et contenant un précurseur de colorant d'oxydation de type para, le 6-méthyl 1-hydroxy 2-aminobenzène ou/et le 4-méthyl 1-amino 2-hydroxybenzène. et un coupleur de formule (I), sont utilisées suivant un procédé mettant en oeuvre la révélation par un agent oxydant.The dye compositions in accordance with the invention and containing a para-type oxidation dye precursor, 6-methyl 1-hydroxy 2-aminobenzene or / and 4-methyl 1-amino 2-hydroxybenzene. and a coupler of formula (I), are used according to a process implementing the development by an oxidizing agent.

Conformément à ce procédé, on mélange au moment de l'emploi, la composition tinctoriale décrite ci-dessus avec une solution oxydante dans une quantite suffisante pour pouvoir développer une coloration, puis on applique le mélange obtenu sur les fibres kératiniques et en particulier les cheveux humains.In accordance with this process, the dye composition described above is mixed at the time of use with an oxidizing solution in an amount sufficient to be able to develop a coloring, then the mixture obtained is applied to the keratin fibers and in particular the hair. humans.

La solution oxydante contient des agents oxydants, tels que l'eau oxygénée, le peroxyde d'urée ou des persels, tels que le persulfate d'ammonium. On utilise de préférence une solution d'eau oxygénée à 20 volumes.The oxidizing solution contains oxidizing agents, such as hydrogen peroxide, urea peroxide or persalts, such as ammonium persulfate. We preferably use a solution of hydrogen peroxide at 20 volumes.

Le mélange obtenu est appliqué sur les cheveux et on laisse poser pendant 10 à 40 minutes, de préférence 15 à 30 minutes, après quoi on rince les cheveux, on les lave au shampooing, on les rince à nouveaux et on les sèche.The mixture obtained is applied to the hair and left to stand for 10 to 40 minutes, preferably 15 to 30 minutes, after which the hair is rinsed, washed with shampoo, rinsed again and dried.

Le coupleur hétérocyclique de formule (I) défini ci-dessus peut également être mis en oeuvre dans un procédé à plusieurs étapes, consistant dans l'une des étapes, à appliquer un précurseur de colorant d'oxydation para, le 6-méthyl 1-hydroxy 2-aminobenzène et/ou le 4-méthyl 1-amino 2-hydroxy benzène et, dans une autre étape, à appliquer le coupleur de formule (I).The heterocyclic coupler of formula (I) defined above can also be used in a multistage process, consisting in one of the stages, in applying a para-oxidation dye precursor, 6-methyl 1- hydroxy 2-aminobenzene and / or 4-methyl 1-amino 2-hydroxy benzene and, in another step, to apply the coupler of formula (I).

L'agent oxydant peut être introduit, tout juste avant l'application, dans la composition appliquée dans le deuxième temps ou bien être additionnée sur les fibres kératiniques elles-mêmes dans un troisième temps, les conditions de pose et de séchage ou de lavage étant identiques.The oxidizing agent can be introduced, just before application, into the composition applied in the second step or else be added to the keratin fibers themselves in a third step, the conditions for laying and drying or washing being identical.

La présente invention a également pour objet l'utilisation d'un composé hétérocyclique de formule (I) défini ci-dessus, à titre de coupleur dans la teinture d'oxydation des fibres kératiniques mettant en oeuvre des précurseurs de colorants d'oxydation de type para ou ortho tels que le 6-méthyl 1-hydroxy 2-aminobenzène et le 4-méthyl 1-amino 2-hydroxybenzène.A subject of the present invention is also the use of a heterocyclic compound of formula (I) defined above, as a coupler in the oxidation dyeing of keratin fibers using oxidation dye precursors of the type para or ortho such as 6-methyl 1-hydroxy 2-aminobenzene and 4-methyl 1-amino 2-hydroxybenzene.

Les exemples suivants sont destinés à illustrer l'invention.The following examples are intended to illustrate the invention.

EXEMPLE DE PREPARATION 1PREPARATION EXAMPLE 1 Préparation du 6-N-β-hydroxyéthylamino indole. Preparation of 6-N-β-hydroxyethylamino indole . Etape 1Step 1 Préparation du 6-N-(β-chloroéthoxycarbonyl)amino indolePreparation of 6-N- (β-chloroethoxycarbonyl) amino indole

On chauffe au reflux 0,05 mole (6,6 g) de 6-amino indole, 5,5 g de carbonate de calcium dans 30 ml de dioxane. On ajoute peu à peu 0,055 mole (7,9 g) de chloroformiate de β-chloréthyle. Le mélange réactionnel est dilué à la glace. Le produit attendu précipite. Il fond à 134°C.0.05 mol (6.6 g) of 6-amino indole, 5.5 g of calcium carbonate in 30 ml of dioxane are heated to reflux. 0.055 mol (7.9 g) of β-chloroethyl chloroformate is gradually added. The reaction mixture is diluted with ice. The expected product precipitates. It melts at 134 ° C.

L'analyse du produit recristallisé de l'éthanol donne les résultats suivants : Analyse pour C₁₁H₁₁N₂O₂Cl C H Cl O N Calculé 55,36 4,65 14,85 13,41 11,74 Trouvé 55,40 4,68 14,72 13,27 11,67 Analysis of the recrystallized product of ethanol gives the following results: Analysis for C₁₁H₁₁N₂O₂Cl VS H Cl O NOT Calculated 55.36 4.65 14.85 13.41 11.74 Find 55.40 4.68 14.72 13.27 11.67

Etape 22nd step Préparation du 6-N-β-hydroxyéthylamino indole. Preparation of 6-N-β-hydroxyethylamino indole .

On ajoute 0,28 mole (66,5 g) de 6-N-(β-chloroéthoxycarbonyl)amino indole à 200 ml de soude 4N et 66,5 ml d'éthanol. Le mélange réactionnel est chauffé 1 heure au reflux. On précipite le produit attendu par ajout de glace. Il fond à 99°C.0.28 mole (66.5 g) of 6-N- (β-chloroethoxycarbonyl) amino indole is added to 200 ml of 4N sodium hydroxide and 66.5 ml of ethanol. The reaction mixture is heated for 1 hour at reflux. The expected product is precipitated by adding ice. It melts at 99 ° C.

L'analyse élémentaire du produit obtenu donne les résultats suivants : Analyse pour C₁₀H₁₂N₂O C H N O Calculé 68,16 6,86 15,90 9,08 Trouvé 67,88 6,91 15,91 9,15 Elementary analysis of the product obtained gives the following results: Analysis for C₁₀H₁₂N₂O VS H NOT O Calculated 68.16 6.86 15.90 9.08 Find 67.88 6.91 15.91 9.15

EXEMPLE DE PREPARATION 2PREPARATION EXAMPLE 2 Préparation du chlorhydrage de 6-N(β-hydroxyéthyl)amino 1-méthyl indole. Preparation of the hydrochlorination of 6-N (β-hydroxyethyl) amino 1-methyl indole . Etape 1Step 1 Préparation de la N-(6-indolyl)oxazolidine-1,3 one-2Preparation of N- (6-indolyl) oxazolidine-1,3 one-2

A 120 ml d'une solution de méthylate de sodium à 30% dans le méthanol, on ajoute 60 ml de méthanol puis, sous agitation, 0,25 mole (60 g) de 6-(β-chloréthoxycarbonyl)amino indole (préparé selon la première étape de l'exemple 1). La température atteint 50°C. L'agitation est maintenue 15 minutes après la fin de l'addition. Le précipité formé est essoré, lavé à l'alcool puis séché. Il fond à 199°C.To 120 ml of a 30% sodium methylate solution in methanol, 60 ml of methanol are added and then, with stirring, 0.25 mole (60 g) of 6- (β-chlorethoxycarbonyl) amino indole (prepared according to the first step of example 1). The temperature reaches 50 ° C. Stirring is continued 15 minutes after the end of the addition. The precipitate formed is drained, washed with alcohol and then dried. It melts at 199 ° C.

L'analyse du produit recristallisé de l'acide acétique donne les résultats suivants : Analyse pour C₁₁H₁₀N₂O₂ C H N O Calculé 65,34 4,98 13,85 15,82 Trouvé 65,42 5,02 13,75 15,86 Analysis of the recrystallized product of acetic acid gives the following results: Analysis for C₁₁H₁₀N₂O₂ VS H NOT O Calculated 65.34 4.98 13.85 15.82 Find 65.42 5.02 13.75 15.86

Etape 22nd step Préparation de la N-[6-(1-méthyl)indolyl]oxazolidine-1,3 one-2Preparation of N- [6- (1-methyl) indolyl] oxazolidine-1,3 one-2

A une solution de 0,15 mole (30,5 g) de N-(6-indolyl)oxazolidine-1,3 one-2 dans 300 ml de diméthylformamide, on ajoute 100 ml d'une solution à 30% de méthylate de sodium dans le méthanol. Le mélange réactionnel est chauffé à 40°C. On ajoute goutte à goutte 28 ml d'iodure de méthyle. Le chauffage est maintenu 1 heure après la fin de l'addition. Après dilution du milieu réactionnel par de l'eau glacée, le produit attendu précipite. Après essorage, lavage à l'eau puis à l'éthanol, il fond à 160°C.To a solution of 0.15 mole (30.5 g) of N- (6-indolyl) oxazolidine-1,3 one-2 in 300 ml of dimethylformamide is added 100 ml of a 30% solution of methyl methoxide sodium in methanol. The reaction mixture is heated to 40 ° C. 28 ml of methyl iodide are added dropwise. Heating is maintained 1 hour after the end of the addition. After dilution of the reaction medium with ice water, the expected product precipitates. After spinning, washing with water and then with ethanol, it melts at 160 ° C.

L'analyse du produit recristallisé de l'acide acétique donne les résultats suivants : Analyse pour C₁₂H₁₂N₂O₂ C H N O Calculé 66,65 5,59 12,95 14,80 Trouvé 66,55 5,62 12,76 15,08 Analysis of the recrystallized product of acetic acid gives the following results: Analysis for C₁₂H₁₂N₂O₂ VS H NOT O Calculated 66.65 5.59 12.95 14.80 Find 66.55 5.62 12.76 15.08

Etape 3Stage 3 Préparation du chlorhydrate de 6-(β-hydroxyéthyl)amino 1-méthyl indole. Preparation of 6- (β-hydroxyethyl) amino 1-methyl indole hydrochloride .

On chauffe 1 heure au reflux 0,02 mole (4,32 g) de N-[6-(1-méthyl)indolyl]oxazolidine-1,3 one-2 dans 17 ml de soude 4N additionnée de 2 ml d'éthanol. Le milieu réactionnel est dilué par de l'eau glacée, puis le produit obtenu est extrait par l'acétate d'éthyle.Heated for 1 hour at reflux 0.02 mol (4.32 g) of N- [6- (1-methyl) indolyl] oxazolidine-1,3 one-2 in 17 ml of 4N sodium hydroxide supplemented with 2 ml of ethanol . The reaction medium is diluted with ice water, then the product obtained is extracted with ethyl acetate.

L'huile obtenue après évaporation de l'acétate d'éthyle est ajoutée à 7 ml d'une solution d'acide chlorhydrique 7M dans l'éthanol. Le produit attendu précipite.The oil obtained after evaporation of the ethyl acetate is added to 7 ml of a solution of 7M hydrochloric acid in ethanol. The expected product precipitates.

L'analyse du produit obtenu après lavage et séchage, donne les résultats suivants : Analyse pour C₁₁H₁₅ClN₂O C H Cl N O Calculé 58,28 6,67 15,64 12,36 7,06 Trouvé 58,16 6,70 15,52 12,45 7,13 Analysis of the product obtained after washing and drying gives the following results: Analysis for C₁₁H₁₅ClN₂O VS H Cl NOT O Calculated 58.28 6.67 15.64 12.36 7.06 Find 58.16 6.70 15.52 12.45 7.13

EXEMPLE DE PREPARATION 3PREPARATION EXAMPLE 3 Préparation du 6-N-(β, γ-dihydroxypropyl)amino indole. Preparation of 6-N- (β, γ-dihydroxypropyl) amino indole .

On dissout 26,4 g de 6-amino indole dans 70 ml d'alcool absolu. On ajoute 29,6 g de glycidol et on agite pendant 4 heures à 30-40°C.26.4 g of 6-amino indole are dissolved in 70 ml of absolute alcohol. 29.6 g of glycidol are added and the mixture is stirred for 4 hours at 30-40 ° C.

On verse sur 200 g d'eau glacée et on extrait par trois fois 100 ml d'acétate d'éthyle. On lave le solvant à l'eau. On le sèche sur Na₂SO₄ et chasse à sec sous vide.Poured into 200 g of ice water and extracted with three times 100 ml of ethyl acetate. The solvent is washed with water. It is dried over Na₂SO₄ and vacuum-dried hunting.

Le résidu huileux est repris trois fois dans 0,6 litre d'éther isopropylique au reflux. On filtre l'éther et on chasse à sec sous vide. On reprend l'huile résiduelle dans 10 cm³ d'acétate d'éthyle et on purifie sur colonne de silice (éluant acétate d'éthyle 9/Heptane 1).The oily residue is taken up three times in 0.6 liters of isopropyl ether at reflux. Filter the ether and vacuum dry. The residual oil is taken up in 10 cm³ of ethyl acetate and purified on a silica column (eluent ethyl acetate 9 / Heptane 1).

La fraction contenant le produit attendu est évaporée à sec sous vide.The fraction containing the expected product is evaporated to dryness under vacuum.

On obtient une huile incolore qui donne les résultats suivants : Analyse pour C₁₁H₁₄N₂O₂ C H N O Calculée 64,06 6,84 13,58 15,51 Trouvé 63,95 6,98 13,48 15,59 A colorless oil is obtained which gives the following results: Analysis for C₁₁H₁₄N₂O₂ VS H NOT O Calculated 64.06 6.84 13.58 15.51 Find 63.95 6.98 13.48 15.59

On prépare les compositions suivantes :

Figure imgb0007
The following compositions are prepared:
Figure imgb0007

Dans tous les exemples qui suivent, les compositions sont mélangées poids par poids avec un oxydant titrant 20 volumes en eau oxygénée et dont le pH est de 3.In all of the examples which follow, the compositions are mixed weight by weight with an oxidizing agent titrating 20 volumes of hydrogen peroxide and whose pH is 3.

Les mélanges ainsi réalisés sont appliqués 30 minutes sur des cheveux gris à 90% de blancs, puis rincés et lavés. Les cheveux sont ensuite séchés.The mixtures thus produced are applied for 30 minutes to gray hair containing 90% white hairs, then rinsed and washed. The hair is then dried.

La nature des colorants, leurs quantités et la couleur obtenue sont indiquées dans les tableaux qui suivent.

Figure imgb0008
Figure imgb0009
 The nature of the dyes, their quantities and the color obtained are indicated in the tables which follow.
Figure imgb0008
Figure imgb0009

EXEMPLE 13EXAMPLE 13

On prépare le mélange tinctorial suivant : - p-phénylènediamine 0,27 g - 6-N-(β, γ-dihydroxypropyl)amino indole 0,52 g - Alcool oléique polyglycérolé à 2 moles de glycérol 4,5 g - Alcool oléique polyglycérolé à 4 moles de glycérol 4,5 g - ETHOMEEN O 12 - Société ARMOON HESS CHEMICAL Ltd (oléylamine oxyéthylénée à 12 modes d'oxyde d'éthylène) 4,5 g - COMPERLAN KD - Société HENKEL (diéthanolamide de coprah) 9,0 g - Propylène glycol 4,0 g - 2-butoxyéthanol 8,0 g - Ethanol à 96° 6,0 g - MASQUOL DTPA - Société PROTEX (sel pentasodique de l'acide diéthylène triamine pentacétique) 2,0 g - Hydroquinone 0,15 g - Solution de bisulfite de sodium à 35° Bé 1,3 g - Ammoniaque à 22° Bé 10,0 g - Eau   qsp 100,0 g - pH = 9,8 The following dye mixture is prepared: - p-phenylenediamine 0.27 g - 6-N- (β, γ-dihydroxypropyl) amino indole 0.52 g - Polyglycerolated oleic alcohol with 2 moles of glycerol 4.5g - Polyglycerolated oleic alcohol with 4 moles of glycerol 4.5g - ETHOMEEN O 12 - ARMOON HESS CHEMICAL Ltd (oxyethylenated oleylamine with 12 modes of ethylene oxide) 4.5g - COMPERLAN KD - HENKEL Company (coconut diethanolamide) 9.0 g - Propylene glycol 4.0g - 2-butoxyethanol 8.0 g - 96 ° ethanol 6.0 g - MASQUOL DTPA - PROTEX Company (pentasodium salt of diethylene triamine pentacetic acid) 2.0 g - Hydroquinone 0.15 g - Sodium bisulfite solution at 35 ° Bé 1.3 g - Ammonia at 22 ° Be 10.0 g - Water qs 100.0 g - pH = 9.8

Au moment de l'emploi, on ajoute 10 g d'eau oxygénée à 20 volumes. Le mélange, appliqué pendant 30 minutes à 30°C sur cheveux décolorés, leur confère, après shampooing et rinçage, une coloration brun rouge.At the time of use, 10 g of hydrogen peroxide are added to 20 volumes. The mixture, applied for 30 minutes at 30 ° C on bleached hair, gives them, after shampooing and rinsing, a reddish brown coloring.

Claims (25)

  1. Oxidation tinctorial composition intended to be used for dyeing keratinous fibres, in particular human keratinous fibres and especially hair, characterized in that it contains, in a solvent medium appropriate for dyeing these fibres, at least one para oxidation dye precursor, 6-methyl-1-hydroxy-2-aminobenzene and/or 4-methyl-1-amino-2-hydroxybenzene and at least one heterocyclic coupler corresponding to the formula (I):
    Figure imgb0019
     in which:
       R₁ and R₃, which may be identical or different, denote a hydrogen atom or a C₁-C₄ alkyl group;
       R₂ denotes a hydrogen atom, a C₁-C₄ alkyl group, a carboxyl group or an alkoxycarbonyl group; at least one of the radicals R₂ or R₃ denoting hydrogen;
       R₄ denotes a hydrogen atom or a C₁-C₄ alkyl or C₁-C₄ hydroxyalkyl or C₂-C₄ polyhydroxyalkyl group;
       the group NHR₄ occupying the positions 4, 6 or 7 of the benzene ring, as well as their salts.
  2. Composition according to Claim 1, characterized in that the para oxidation dye precursors are chosen from para-phenylenediamines, para-aminophenols, para heterocyclic precursors derived from pyridine or pyrimidine, and double bases.
  3. Composition according to Claim 2, characterized in that the para-phenylenediamines are chosen from the compounds corresponding to the formula (II):
    Figure imgb0020
     in which:
       R₅, R₆ and R₇, which may be identical or different, represent a hydrogen or halogen atom, an alkyl radical or an alkoxy radical; and
       R₈ and R₉, which may be identical or different, represent a hydrogen atom or an alkyl, hydroxyalkyl, alkoxyalkyl, carbamylalkyl, mesylaminoalkyl, acetylaminoalkyl, ureidoalkyl, carbalkoxyaminoalkyl, piperidinoalkyl or morpholinoalkyl radical; or R₈ and R₉ form, together with the nitrogen atom to which they are bonded, a piperidino or morpholino heterocycle, with the proviso that R₅ or R₇ represents a hydrogen atom when R₈ and R₉ do not represent a hydrogen atom;
       and also the salts of these compounds.
  4. Composition according to any one of Claims 1 to 3, characterized in that the heterocyclic couplers of formula (I) are chosen from 6-aminoindole, 7-aminoindole, 6-N-β-hydroxyethylaminoindole, 6-N-β-hydroxyethylamino-1-methylindole, 6-methylaminoindole, 6-amino-N-methyl-indole, 6-amino-2-carboxyindole, 6-amino-3-methylindole, 6-amino-2-methylindole, 6-amino-2-ethoxycarbonylindole and 6-N(β,γ-dihydroxypropyl)aminoindole.
  5. Composition according to Claim 3, characterized in that the para-phenylenediamines are chosen from p-phenylenediamine, p-toluylenediamine, methoxy-para-phenylenediamine, 2,6-dimethyl-p-phenylenediamine, 2,5-dimethyl-p-phenylenediamine, 2-methyl-5-methoxy-para-phenylenediamine, 2,6-dimethyl-5-methoxy-p-phenylenediamine, N,N-dimethyl-para-phenylenediamine, 3-methyl-4-amino-N,N-diethylaniline, N,N-di(β-hydroxyethyl)-para-phenylenediamine, 3-methyl-4-amino-N,N-di(β-hydroxyethyl)aniline, 3-chloro-4-amino-N,N-di(β-hydroxyethyl)aniline, 4-amino-N,N-(ethylcarbamylmethyl)aniline, 3-methyl-4-amino-N,N-(ethylcarbamylmethyl)aniline, 4-amino-N,N-(ethyl-β-piperidinoethyl)aniline, 3-methyl-4-amino-N,N-(ethyl-β-piperidinoethyl)aniline, 4-amino-N,N-(ethyl-β-morpholinoethyl)aniline, 3-methyl-4-amino-N,N-(ethyl-β-morpholinoethyl)aniline, 4-amino-N,N-(ethyl-β-acetylaminoethyl)aniline, 4-amino-N-(β-methoxy-ethyl)aniline, 3-methyl-4-amino-N,N-(ethyl-β-acetylaminoethyl)aniline, 4-amino-N,N-(ethyl-β-mesylaminoethyl)aniline, 3-methyl-4-amino-N,N-(ethyl-β-mesylaminoethyl)aniline,4-amino-N,N-(ethyl-β-sulphoethyl)aniline, 3-methyl-4-amino-N,N-(ethyl-β-sulphoethyl)aniline, N-[(4'-amino)phenyl]-morpholine and N-[(4'-amino)phenyl]piperidine and their salts.
  6. Composition according to Claim 2, characterized in that the p-aminophenols are chosen from p-aminophenol, 2-methyl-4-aminophenol, 3-methyl-4-aminophenol, 2-chloro-4-aminophenol, 3-chloro-4-aminophenol, 2,6-dimethyl-4-aminophenol, 3,5-dimethyl-4-aminophenol, 2,3-dimethyl-4-aminophenol, 2,5-dimethyl-4-aminophenol, 2-hydroxymethyl-4-aminophenol, 2-(β-hydroxyethyl)-4-aminophenol, 2-methoxy-4-aminophenol, 3-methoxy-4-aminophenol and 2-methoxymethyl-4-aminophenol.
  7. Composition according to Claim 2, characterized in that the so-called double bases are bis-phenylalkylenediamines corresponding to the formula:
    Figure imgb0021
     in which:
       Z₁ and Z₂, which may be identical or different, represent hydroxyl or NHR₃ groups, where R₃ denotes a hydrogen atom or a lower alkyl radical;
       R₁ and R₂, which may be identical or different, represent either hydrogen atoms or halogen atoms or alkyl groups;
       R represents a hydrogen atom or an alkyl, hydroxyalkyl or aminoalkyl group, in which the amino radical can be substituted;
       and Y represents a radical taken from the group comprising the following radicals: -(CH₂)n-, (CH₂)n,-O-(CH₂)n,-,-(CH₂)n,-CHOH-(CH₂)n,
    Figure imgb0022
     -N-(CH₂)n,-; n being an integer between 0 and 8 and n' being an integer between 0 and 4, it being possible for this base to be in the form of its addition salts with acids.
  8. Composition according to Claim 7, characterized in that the double bases are chosen from N,N'-bis(β-hydroxyethyl)-N,N'-bis(4'-aminophenyl)-1,3-diaminopropan2-ol, N,N'-bis(β-hydroxyethyl)-N,N'-bis(4'-aminophenyl)-ethylenediamine, N,N'-bis(4-aminophenyl)tetramethylenediamine, N,N'-bis(β-hydroxyethyl)-N,N'-bis(4-aminophenyl)tetramethylenediamine, N,N'-bis(4-methylaminophenyl)tetramethylenediamine and N,N'-bis(ethyl)-N,N'-bis(4'-amino-3'-methylphenyl)ethylenediamine.
  9. Composition according to any one of Claims 1 to 8, characterized in that, in addition to the heterocyclic coupler corresponding to the formula (I), the composition contains other couplers known per se, such as meta-diphenols, meta-aminophenols, meta-phenylenediamines, meta-acylaminophenols, meta-ureidophenols, meta-carbalkoxyaminophenols, α-naphthol and couplers having an active methylene group, chosen from the β-ketone compounds and the pyrazolones.
  10. Composition according to Claim 9, characterized in that the supplementary coupler is chosen from 2,4-dihydroxyphenoxyethanol, 2,4-dihydroxyanisole, metaaminophenol, resorcinol monomethyl ether, 2-methyl-5-aminophenol, 2-methyl-5-N-(β-hydroxyethyl)aminophenol, 2-methyl-5-N-(β-mesylaminoethyl)aminophenol, 2,6-dimethyl-3-aminophenol, 6-hydroxybenzomorpholine, 2,4-diaminoanisole, 2,4-diaminophenoxyethanol, 6-aminobenzomorpholine, 2-[N-(β-hydroxyethyl)-amino-4-amino]-phenoxyethanol, 2-amino-4-N-(β-hydroxyethyl)aminoanisole, 2,4-diaminophenyl β,γ-dihydroxypropyl ether, 2,4-diaminophenoxyethylamine and their salts.
  11. Composition according to any one of Claims 1 to 10, characterized in that the composition also contains direct dyes chosen from azo or anthraquinone dyes or the nitro derivatives of the benzene series.
  12. Composition according to any one of Claims 1 to 11, characterized in that the oxidation dye precursors of the para type and the couplers are present, as a whole, in the composition in proportions of from 0.3 to 7% by weight relative to the total weight of the composition.
  13. Composition according to any one of Claims 1 to 12, characterized in that the composition contains the coupler of formula (I) in proportions of between 0.05 and 3.5% by weight relative to the total weight of the composition.
  14. Composition according to any one of Claims 1 to 13, characterized in that the solvent medium appropriate for dyeing is aqueous and in that its pH is between 8 and 11.
  15. Composition according to any one of Claims 1 to 14, characterized in that it also contains anionic, cationic, nonionic or amphoteric surfactants or their mixtures, in proportions of between 0.5 and 55% by weight, and preferably between 2 and 50% by weight, relative to the total weight of the composition.
  16. Composition according to any one of Claims 1 to 15, characterized in that the composition contains organic solvents chosen from C₁-C₄ lower alkanols, glycerol, glycols or glycol ethers and aromatic alcohols in proportions of between 1 and 40% by weight.
  17. Composition according to any one of Claims 1 to 16, characterized in that it also contains thickeners in proportions of between 0.1 and 5% by weight relative to the total weight of the composition.
  18. Composition according to any one of Claims 1 to 17, characterized in that it also contains antioxidants in proportions of between 0.05 and 1.5% by weight relative to the total weight of the composition.
  19. Method for dyeing keratinous fibres, characterized in that a para oxidation dye precursor 6-methyl-1-hydroxy-2-aminobenzene and/or 4-methyl-1-amino-2-hydroxybenzene and at least one coupler corresponding to the formula (I):
    Figure imgb0023
     in which:
       R₁ and R₃, which may be identical or different, denote a hydrogen atom or a C₁-C₄ alkyl group;
       R₂ denotes a hydrogen atom, a C₁-C₄ alkyl group, a carboxyl group or an alkoxycarbonyl group;
       R₄ denotes a hydrogen atom or a C₁-C₄ alkyl or C₁-C₄ hydroxyalkyl or C₂-C₄ polyhydroxyalkyl group;
       the group NHR₄ occupying the positions 4, 6 or 7 of the benzene ring, as well as their salts in a solvent medium appropriate for dyeing are applied to the keratinous fibres, in particular human keratinous fibres and especially hair, said precursor and coupler being mixed at the time of use with an oxidant in an amount sufficient to be able to develop a colouring.
  20. Method according to Claim 19, characterized in that the mixture is kept in contact with the fibres for 10 to 40 minutes, and preferably 15 to 30 minutes, after which the fibres are rinsed, washed, rinsed again and dried.
  21. Compound, characterized in that it corresponds to the formula:
    Figure imgb0024
     in which:
       R₁ and R₃, independently of one another, represent a hydrogen atom or a C₁-C₄ alkyl group;
       R₂ denotes hydrogen or a C₁-C₄ alkyl group or a carboxyl or alkoxycarbonyl group; and
       R₄ represents a C₁-C₄ alkyl, C₁-C₄ hydroxyalkyl or C₂-C₄ polyhydroxyalkyl group, NHR₄ occupying the positions 4, 6 or 7 and R₄ not being able to denote C₁-C₄ alkyl when NHR₄ is in position 4.
  22. Use of the compound corresponding to the formula:
    Figure imgb0025
     in which:
       R₁ and R₃, which may be identical or different, denote a hydrogen atom or a C₁-C₄ alkyl group;
       R₂ denotes a hydrogen atom, a C₁-C₄ alkyl group, a carboxyl group or an alkoxycarbonyl group; at least one of the radicals R₂ or R₃ denoting hydrogen;
       R₄ denotes a hydrogen atom or a C₁-C₄ alkyl or C₁-C₄ hydroxyalkyl or C₂-C₄ polyhydroxyalkyl group;
       the group NHR₄ occupying the positions 4, 6 or 7 of the benzene ring, as well as their salts, as coupler in the oxidation dyeing of keratinous fibres using oxidation dye precursors of the para type or 6-methyl-1-hydroxy-2-aminobenzene and/or 4-methyl-1-amino-2-hydroxybenzene.
  23. Method for dyeing keratinous fibres, characterized in that, in a first step, the para oxidation dye precursor or 6-methyl-1-hydroxy-2-aminobenzene and/or 4-methyl-1-amino-2-hydroxybenzene are applied for 10 to 40 minutes and then, in a second step, the coupler of formula (I) defined in Claim 1 is applied for 10 to 40 minutes, the oxidant being present in the composition applied in the second step or being applied to the fibres themselves during a third step.
  24. Oxidation tinctorial composition intended to be used for dyeing keratinous fibres, in particular human keratinous fibres and especially hair, characterized in that it contains, in a solvent medium appropriate for dyeing these fibres, at least 6-methyl-1-hydroxy-2-aminobenzene or 4-methyl-1-amino-2-hydroxybenzene and at least one heterocyclic coupler corresponding to the formula (I):
    Figure imgb0026
     in which:
       R₁ and R₃, which may be identical or different, denote a hydrogen atom or a C₁-C₄ alkyl group;
       R₂ denotes a hydrogen atom, a C₁-C₄ alkyl group, a carboxyl group or an alkoxycarbonyl group; at least one of the radicals R₂ or R₃ denoting hydrogen;
       R₄ denotes a hydrogen atom or a C₁-C₄ alkyl or C₁-C₄ hydroxyalkyl or C₂-C₄ polyhydroxyalkyl group;
       the group NHR₄ occupying the positions 4, 6 or 7 of the benzene ring, as well as their salts.
  25. Method for dyeing keratinous fibres, characterized in that at least 6-methyl-1-hydroxy-2-aminobenzene or 4-methyl-1-amino-2-hydroxybenzene and at least one heterocyclic coupler corresponding to the formula (I):
    Figure imgb0027
     in which:
       R₁ and R₃, which may be identical or different, denote a hydrogen atom or a C₁-C₄ alkyl group;
       R₂ denotes a hydrogen atom, a C₁-C₄ alkyl group, a carboxyl group or an alkoxycarbonyl group; at least one of the radicals R₂ or R₃ denoting hydrogen;
       R₄ denotes a hydrogen atom or a C₁-C₄ alkyl or C₁-C₄ hydroxyalkyl or C₂-C₄ polyhydroxyalkyl group;
       the group NHR₄ occupying the positions 4, 6 or 7 of the benzene ring, as well as their salts in a solvent medium appropriate for dyeing are applied to the keratinous fibres, in particular human keratinous fibres and especially hair, said precursor and coupler being mixed at the time of use with an oxidant in an amount sufficient to be able to develop a colouring,
       the mixture is kept in contact with the fibres for 10 to 40 minutes, and preferably 15 to 30 minutes, after which the fibres are rinsed, washed, rinsed again and dried.
EP90402928A 1989-10-20 1990-10-18 Dyeing composition containing oxidation dyes precursors and aminoindole derivatives as coupling agent Expired - Lifetime EP0424261B1 (en)

Applications Claiming Priority (2)

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LU87611A LU87611A1 (en) 1989-10-20 1989-10-20 TINCTORIAL COMPOSITION FOR KERATINIC FIBERS CONTAINING OXIDATION DYE PRECURSORS AND AMINO INDOLIC COUPLERS, DYEING METHODS USING SAID COMPOSITIONS AND COMPOUNDS
LU87611 1989-10-20

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EP0424261A1 EP0424261A1 (en) 1991-04-24
EP0424261B1 true EP0424261B1 (en) 1996-01-03

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US7288124B2 (en) 2004-09-08 2007-10-30 L'oreal S.A. Heteroaromatic binuclear black direct dyes
US7879113B2 (en) 2008-12-19 2011-02-01 L'oreal S.A. Composition comprising at least one fatty substance and at least one silicate, dyeing or lightening process using it and devices or kits therefor
US7901464B2 (en) 2007-12-21 2011-03-08 L'oreal S.A. Process for lightening direct dyeing or oxidation dyeing in the presence of at least one organic amine, device therefor and anhydrous composition
US7909888B2 (en) 2008-12-19 2011-03-22 L'oreal Process for dyeing or lightening human keratin fibers using an anhydrous composition and a monoethanolamine/basic amino acid mixture, and suitable device therefor
US7909887B2 (en) 2007-12-21 2011-03-22 L'oreal S.A. Method for dyeing in the presence of at least one oxidizing agent and at least one organic amine, device for use thereof and ready-to-use composition
US7914591B2 (en) 2008-12-19 2011-03-29 L'oreal S.A. Process for the lightening dyeing of keratin materials using at least one anhydrous dyeing composition comprising at least one alkaline agent and at least one oxidizing composition
US7918903B2 (en) 2008-12-19 2011-04-05 L'oreal, S.A. Composition for the oxidation dyeing of keratin fibers comprising at least one fatty substance and at least one N,N bis(beta-hydroxyethyl)-para-phenylenediamine
US7918902B2 (en) 2008-12-19 2011-04-05 L'oreal S.A. Process for lightening or process for direct dyeing or oxidation dyeing of keratin fibers in the presence of at least one ammonium salt and device therefor
US7922777B2 (en) 2008-12-19 2011-04-12 L'ORéAL S.A. Lightening and dyeing of human keratin fibers using an anhydrous composition comprising a monoethyanolamine/basic amino acid mixture, and device therefor
US7927381B2 (en) 2008-12-19 2011-04-19 L'oreal S.A. Process for lightening or lightening direct dyeing or oxidation dyeing in the presence of an aqueous composition comprising at least one fatty substance, and device
US7927383B2 (en) 2008-12-19 2011-04-19 L'oreal S.A. Composition comprising at least one fatty substance and at least one surfactant comprising ethylene oxide, dyeing or lightening process using it and devices therefor
US7927380B2 (en) 2008-12-19 2011-04-19 L'oreal S.A. Composition for oxidation dyeing of keratin fibers comprising at least one fatty substance, at least one oxidation base, at least one dye precursor, at least one oxidizing agent, and optionally at least one alkaline agent, and processes and kits therewith
US7927382B2 (en) 2008-12-19 2011-04-19 L'oreal S.A. Ready-to-use composition for the oxidation dyeing of keratin fibers comprising at least one fatty substance, at least one oxidation chosen from 4,5-diaminopyrazoles and acid addition salts thereof, at least one additional dye precursor other than the at least one oxidation base, at least one oxidizing agent, and optionally at least one alkaline agent, and processes and kits therewith
US7931698B2 (en) 2008-12-19 2011-04-26 L'oreal S.A. Ready-to-use composition for oxidation dyeing of keratin fibers comprising at least one fatty substance, at least one thickener, at least one dye precursor, at least one oxidizing agent, and at least one alkaline agent, and process and kits therewith
US7935154B2 (en) 2008-12-19 2011-05-03 L'oreal S.A. Process for lightening or lightening direct dyeing or oxidation dyeing in the presence of at least one organic amine and at least one inorganic base, and device therefor
US7947089B2 (en) 2008-12-19 2011-05-24 L'oreal S.A. Method of coloring or lightening in the presence of an inorganic base and kit
US7981165B2 (en) 2008-12-19 2011-07-19 L'oreal S.A. Process for lightening keratin materials using an anhydrous composition comprising at least one fatty substance and at least one alkaline agent, and at least one oxidizing composition
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US8066781B2 (en) 2008-12-19 2011-11-29 L'oreal S.A. Composition comprising at least one fatty substance and at least one cationic polymer, dyeing or lightening process using it and devices therefor
US8070831B2 (en) 2008-12-19 2011-12-06 L'oreal S.A. Composition comprising at least one solid fatty alcohol, dyeing or lightening process using same and devices
US8092553B2 (en) 2008-12-19 2012-01-10 L'oreal S.A. Composition for the oxidation dyeing of keratin fibers comprising para-aminophenol, dipropylene glycol and at least one additional dye precursor
US8114170B2 (en) 2009-12-22 2012-02-14 L'oreal S.A. Agent for coloring and/or bleaching keratin fibers comprising composition (A), composition (B), at least one fat and at least one reductone
US8118884B2 (en) 2009-12-22 2012-02-21 L'oreal S.A. Dyeing or lightening compositions comprising at least one fatty substance and at least one amphoteric polymer
US8142518B2 (en) 2009-12-22 2012-03-27 L'oreal Agent for dyeing and/or bleaching keratin fibers in two parts, comprising at least one fatty substance and at least one sequestrant
US8147564B2 (en) 2009-12-22 2012-04-03 L'oreal Agent for dyeing and/or bleaching keratin fibers, comprising composition (A), anhydrous composition (B), and at least one fatty substance
US8262739B2 (en) 2008-12-19 2012-09-11 L'oreal S.A. Hair treatment process using a direct emulsion comprising an oxidizing agent and a composition containing an alkaline agent
US8889110B2 (en) 2008-12-19 2014-11-18 L'oreal Oxidizing composition for the treatment of keratin fibers comprising at least one oil, at least one fatty alcohol and at least one oxyalkylenated fatty alcohol
US9005594B2 (en) 2007-12-21 2015-04-14 L'oreal Method for lightening human keratin fibers using at least one anhydrous composition, at least one organic amine, and at least one oxidizing agent, and device for use thereof
US9017424B2 (en) 2008-12-19 2015-04-28 L'oreal Process for lightening keratin materials using an emulsion comprising an alkaline agent and an oxidizing composition

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* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US5752982A (en) * 1991-03-28 1998-05-19 L'oreal Methods for dyeing keratinous fibers with compositions which contain aminoindole couplers, oxidation dye precursors, and oxidizing agents at acid pHs
FR2674431A1 (en) * 1991-03-28 1992-10-02 Oreal PROCESS FOR DYING KERATINOUS FIBERS WITH AMINOINDOLES, PHASE ACID AND COMPOSITIONS THEREFOR.
FR2675380A1 (en) * 1991-04-18 1992-10-23 Oreal PROCESS FOR DYING KERATIN FIBERS WITH AMINOINDOLES, BASIC PH, COMPOSITIONS IMPLEMENTED AND NOVEL COMPOUNDS.
US5938792A (en) * 1991-04-18 1999-08-17 L'oreal Process for dyeing keratinous fibers with aminoindoles and oxidation dye precursors at basic Ph's and dyeing agents
US6569211B2 (en) 1991-11-19 2003-05-27 Henkel Kommanditgesellschaft Auf Aktien 5,6-dihydroxyindolines as additives for hair dyeing preparations
FR2687570A1 (en) * 1992-02-21 1993-08-27 Oreal COSMETIC COMPOSITION BASED ON NON-IONIC SURFACTANT AGENTS AND CATIONIC OR AMPHOTERIC SUBSTANTIVE POLYMERS AND ITS USE AS A DYE OR DECOLORATION SUPPORT.
DE4418533C2 (en) * 1994-05-27 1996-04-11 Hunger Walter Dr Ing E H Fifth wheel coupling, method for producing a fifth wheel coupling and use of a plate
FR2722687A1 (en) 1994-07-22 1996-01-26 Oreal Non-ionic or cationic modified guar gum as sole thickener in hair dye compsns.
FR2730924B1 (en) * 1995-02-27 1997-04-04 Oreal KERATINIC FIBER OXIDATION DYE COMPOSITION COMPRISING A DIAMINOPYRAZOLE DERIVATIVE AND A HETEROCYCLIC COUPLER AND DYEING METHOD
US5849042A (en) * 1997-11-19 1998-12-15 Bristol-Myers Squibb Hair dye compositions containing 2,3 dialkyl-4-aminophenol and a 2-alkyl-1-naphthol
HUP0102869A2 (en) 1998-06-23 2002-02-28 Henkel Kommanditgesellschaft Auf Aktien Colorant for colouring keratin fibres
FR2786094B1 (en) * 1998-11-20 2001-01-12 Oreal KERATINIC FIBER OXIDATION DYE COMPOSITION AND DYEING METHOD USING THE SAME
FR2805737B1 (en) * 2000-03-06 2003-01-03 Oreal KERATINIC FIBER OXIDATION DYE COMPOSITION AND DYEING METHOD USING THE SAME
US20100074949A1 (en) 2008-08-13 2010-03-25 William Rowe Pharmaceutical composition and administration thereof
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US20090105272A1 (en) * 2005-12-24 2009-04-23 Grootenhuis Peter D J Prodrugs of modulators of ABC transporters
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Family Cites Families (9)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
AT277464B (en) * 1967-11-06 1969-12-29 Therachemie Chem Therapeut Hair dyes
LU56102A1 (en) * 1968-05-17 1970-01-14
US4013404A (en) * 1970-12-06 1977-03-22 American Cyanamid Company Method of dyeing hair with indolines, indoles and indazoles
LU77994A1 (en) * 1977-08-19 1979-05-23 Oreal TINCTORIAL COMPOSITIONS BASED ON OXIDIZING COLORANTS CONTAINING AN ALKANOIC ACID (2,5-DIHYDROXYPHENYL) OR ONE OF ITS SALTS AS AN ANTI-OXIDANT AND PROCESS OF PREPARATION
FR2421606A1 (en) * 1978-04-06 1979-11-02 Oreal TWO-STAGE KERATINIC FIBER DYING PROCESS
FR2421607A1 (en) * 1978-04-06 1979-11-02 Oreal TWO-STAGE KERATINIC FIBER DYING PROCESS BY PH VARIATION
US4675332A (en) * 1984-12-10 1987-06-23 Warner-Lambert Company Acidic tetrazolyl substituted indole compounds and their use as antiallergy agents
US4776857A (en) * 1986-11-21 1988-10-11 Repligen Corporation Use of hydroxylated indoles as dye precursors
US4932977A (en) * 1988-11-21 1990-06-12 Clairol Incorporated Indole-aldehyde hair dyes

Cited By (30)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US7288124B2 (en) 2004-09-08 2007-10-30 L'oreal S.A. Heteroaromatic binuclear black direct dyes
US7909887B2 (en) 2007-12-21 2011-03-22 L'oreal S.A. Method for dyeing in the presence of at least one oxidizing agent and at least one organic amine, device for use thereof and ready-to-use composition
US9005594B2 (en) 2007-12-21 2015-04-14 L'oreal Method for lightening human keratin fibers using at least one anhydrous composition, at least one organic amine, and at least one oxidizing agent, and device for use thereof
US7901464B2 (en) 2007-12-21 2011-03-08 L'oreal S.A. Process for lightening direct dyeing or oxidation dyeing in the presence of at least one organic amine, device therefor and anhydrous composition
US7935154B2 (en) 2008-12-19 2011-05-03 L'oreal S.A. Process for lightening or lightening direct dyeing or oxidation dyeing in the presence of at least one organic amine and at least one inorganic base, and device therefor
US7988738B2 (en) 2008-12-19 2011-08-02 L'oreal S.A. Process for the lightening dyeing of keratin materials using an emulsion comprising a dye and an alkaline agent and an oxidizing composition
US7918903B2 (en) 2008-12-19 2011-04-05 L'oreal, S.A. Composition for the oxidation dyeing of keratin fibers comprising at least one fatty substance and at least one N,N bis(beta-hydroxyethyl)-para-phenylenediamine
US7918902B2 (en) 2008-12-19 2011-04-05 L'oreal S.A. Process for lightening or process for direct dyeing or oxidation dyeing of keratin fibers in the presence of at least one ammonium salt and device therefor
US7922777B2 (en) 2008-12-19 2011-04-12 L'ORéAL S.A. Lightening and dyeing of human keratin fibers using an anhydrous composition comprising a monoethyanolamine/basic amino acid mixture, and device therefor
US7927381B2 (en) 2008-12-19 2011-04-19 L'oreal S.A. Process for lightening or lightening direct dyeing or oxidation dyeing in the presence of an aqueous composition comprising at least one fatty substance, and device
US7927383B2 (en) 2008-12-19 2011-04-19 L'oreal S.A. Composition comprising at least one fatty substance and at least one surfactant comprising ethylene oxide, dyeing or lightening process using it and devices therefor
US7927380B2 (en) 2008-12-19 2011-04-19 L'oreal S.A. Composition for oxidation dyeing of keratin fibers comprising at least one fatty substance, at least one oxidation base, at least one dye precursor, at least one oxidizing agent, and optionally at least one alkaline agent, and processes and kits therewith
US7927382B2 (en) 2008-12-19 2011-04-19 L'oreal S.A. Ready-to-use composition for the oxidation dyeing of keratin fibers comprising at least one fatty substance, at least one oxidation chosen from 4,5-diaminopyrazoles and acid addition salts thereof, at least one additional dye precursor other than the at least one oxidation base, at least one oxidizing agent, and optionally at least one alkaline agent, and processes and kits therewith
US7931698B2 (en) 2008-12-19 2011-04-26 L'oreal S.A. Ready-to-use composition for oxidation dyeing of keratin fibers comprising at least one fatty substance, at least one thickener, at least one dye precursor, at least one oxidizing agent, and at least one alkaline agent, and process and kits therewith
US7909888B2 (en) 2008-12-19 2011-03-22 L'oreal Process for dyeing or lightening human keratin fibers using an anhydrous composition and a monoethanolamine/basic amino acid mixture, and suitable device therefor
US7947089B2 (en) 2008-12-19 2011-05-24 L'oreal S.A. Method of coloring or lightening in the presence of an inorganic base and kit
US7981165B2 (en) 2008-12-19 2011-07-19 L'oreal S.A. Process for lightening keratin materials using an anhydrous composition comprising at least one fatty substance and at least one alkaline agent, and at least one oxidizing composition
US7914591B2 (en) 2008-12-19 2011-03-29 L'oreal S.A. Process for the lightening dyeing of keratin materials using at least one anhydrous dyeing composition comprising at least one alkaline agent and at least one oxidizing composition
US7988737B2 (en) 2008-12-19 2011-08-02 L'oreal S.A. Ready-to-use composition for oxidation dyeing of keratin fibers comprising at least one fatty substance chosen from fatty amides and fatty acid esters, at least one dye precursor, at least one oxidizing agent and optionally at least one alkaline agent, and methods and kits therewith
US8066781B2 (en) 2008-12-19 2011-11-29 L'oreal S.A. Composition comprising at least one fatty substance and at least one cationic polymer, dyeing or lightening process using it and devices therefor
US8070831B2 (en) 2008-12-19 2011-12-06 L'oreal S.A. Composition comprising at least one solid fatty alcohol, dyeing or lightening process using same and devices
US8092553B2 (en) 2008-12-19 2012-01-10 L'oreal S.A. Composition for the oxidation dyeing of keratin fibers comprising para-aminophenol, dipropylene glycol and at least one additional dye precursor
US9017424B2 (en) 2008-12-19 2015-04-28 L'oreal Process for lightening keratin materials using an emulsion comprising an alkaline agent and an oxidizing composition
US7879113B2 (en) 2008-12-19 2011-02-01 L'oreal S.A. Composition comprising at least one fatty substance and at least one silicate, dyeing or lightening process using it and devices or kits therefor
US8889110B2 (en) 2008-12-19 2014-11-18 L'oreal Oxidizing composition for the treatment of keratin fibers comprising at least one oil, at least one fatty alcohol and at least one oxyalkylenated fatty alcohol
US8262739B2 (en) 2008-12-19 2012-09-11 L'oreal S.A. Hair treatment process using a direct emulsion comprising an oxidizing agent and a composition containing an alkaline agent
US8147564B2 (en) 2009-12-22 2012-04-03 L'oreal Agent for dyeing and/or bleaching keratin fibers, comprising composition (A), anhydrous composition (B), and at least one fatty substance
US8142518B2 (en) 2009-12-22 2012-03-27 L'oreal Agent for dyeing and/or bleaching keratin fibers in two parts, comprising at least one fatty substance and at least one sequestrant
US8118884B2 (en) 2009-12-22 2012-02-21 L'oreal S.A. Dyeing or lightening compositions comprising at least one fatty substance and at least one amphoteric polymer
US8114170B2 (en) 2009-12-22 2012-02-14 L'oreal S.A. Agent for coloring and/or bleaching keratin fibers comprising composition (A), composition (B), at least one fat and at least one reductone

Also Published As

Publication number Publication date
US5364414A (en) 1994-11-15
CN1051670A (en) 1991-05-29
JPH03193725A (en) 1991-08-23
DK0424261T3 (en) 1996-05-13
KR910007500A (en) 1991-05-30
KR0185984B1 (en) 1999-05-01
AU6479190A (en) 1991-04-26
DE69024597D1 (en) 1996-02-15
LU87611A1 (en) 1991-05-07
CA2028236A1 (en) 1991-04-21
ZA908397B (en) 1991-08-28
DE69024597T2 (en) 1996-05-15
AU642916B2 (en) 1993-11-04
GR3019511T3 (en) 1996-07-31
JP3165434B2 (en) 2001-05-14
BR9005288A (en) 1991-09-17
ES2081358T3 (en) 1996-03-01
EP0424261A1 (en) 1991-04-24
ATE132363T1 (en) 1996-01-15

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